CN117003212B - Preparation method of battery grade material - Google Patents
Preparation method of battery grade material Download PDFInfo
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- CN117003212B CN117003212B CN202310987675.9A CN202310987675A CN117003212B CN 117003212 B CN117003212 B CN 117003212B CN 202310987675 A CN202310987675 A CN 202310987675A CN 117003212 B CN117003212 B CN 117003212B
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- nickel
- iron
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 title abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 136
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 67
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 61
- 239000000706 filtrate Substances 0.000 claims abstract description 51
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 49
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 49
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 41
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 41
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 238000005260 corrosion Methods 0.000 claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 21
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 25
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000009854 hydrometallurgy Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 239000000047 product Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 229910000863 Ferronickel Inorganic materials 0.000 description 15
- 238000006056 electrooxidation reaction Methods 0.000 description 14
- -1 ammonium ions Chemical class 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000008429 bread Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/06—Etching of iron or steel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method of battery grade material ferric phosphate and nickel sulfate, which comprises the following steps: (1) Corroding and dissolving the alloy containing nickel and iron in electrolyte containing ammonium sulfate by adopting an electric auxiliary corrosion mode; (2) After the electric auxiliary corrosion is completed, filtering the electrolyte to obtain filtrate; (3) Adjusting the pH value of the filtrate obtained in the step (2), aerating, adding ammonium phosphate salt to generate ferric phosphate dihydrate precipitate, and filtering to obtain filtrate and ferric phosphate dihydrate; (4) Adjusting the pH value of the filtrate obtained in the step (3), and filtering to remove impurity precipitate to obtain filtrate; (5) Regulating the pH value of the filtrate obtained in the step (4), and evaporating to dryness to obtain residues; (6) acidolysis of the residue obtained in the step (5) to obtain a solution; (7) And (3) evaporating and crystallizing the solution obtained in the step (6) to obtain nickel sulfate. The invention adopts a hydrometallurgy process to simultaneously produce two high-value battery raw materials: battery grade nickel sulfate and iron phosphate.
Description
Technical Field
The invention belongs to the field of battery material preparation, and particularly relates to a method for preparing battery-grade ferric phosphate and nickel sulfate products.
Background
With the gradual popularization of new energy automobiles, the prices of ternary materials and lithium iron phosphate materials related to the new energy automobiles are increased, and especially with the continuous innovative research of high-nickel batteries, the shortage of nickel resources becomes obvious in the domestic market. The Gansu Jinchuan of China has large nickel sulfide ores, the whole nickel sulfide ores are nickel clean importation countries, and the nickel salt and the metal nickel always have inverted prices under the same metal quantity due to the requirements of stainless steel and a ternary battery on nickel, so that the value of one metal ton of nickel is different by more than 2 ten thousand.
The laterite-nickel ore smelting semi-finished product comprises ferronickel, mixed cobalt nickel hydroxide and the like. Ferronickel has become a constant type in the industry for stainless steel smelting and cobalt nickel hydroxide mixed for battery grade material preparation, but the explosive growth of new energy storage batteries requires more nickel resources. The wet refining of battery grade nickel sulfate with mixed cobalt nickel hydroxide product as material is limited by the front-end material feeding scale, and the gap is needed to be supplemented with better nickel resource.
The industry has studied the method for preparing nickel iron into nickel sulfate by adopting water-quenched nickel as a raw material and adopting a normal-pressure and high-pressure leaching wet smelting process, but the process flow is long, iron resources are not fully utilized, and the problem of massive overflow of hydrogen sulfide is faced when water-quenched nickel acid is dissolved. Meanwhile, when customs declares, the water quenched nickel and the nickel-iron tax collection amount differ by 20 percent.
The price of nickel iron per ton of nickel in the market is about six nickel price, and iron is not counted; the content of other impurity components except iron, nickel and silicon dioxide in the ferronickel is not more than 1.5 percent. The nickel-iron is treated by adopting a wet smelting process to produce battery-grade ferric phosphate and nickel sulfate, so that the nicks of nickel and iron resources in the power battery industry can be supplemented, and the industrial value of the nickel-iron is improved more. At present, a plurality of researches are conducted on the direction of recovering ferric phosphate and nickel sulfate by hydrometallurgical ferronickel, but the method has disadvantages. For example, battery grade iron phosphate and nickel sulfate cannot be obtained simultaneously, and harmful gas is generated.
Therefore, there is a need to develop a method for preparing battery grade iron phosphate and nickel sulfate, which can use an alloy containing nickel and iron as a raw material, is low in cost, and does not produce harmful gases.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of battery-grade ferric phosphate and nickel sulfate. The invention fully dissolves the alloy containing nickel and iron through electrolytic corrosion dissolution, and hydrogen sulfide is not produced; adding ammonium phosphate salt during iron precipitation, and separating ferric phosphate dihydrate and nickel ammonia solution by utilizing the property that ferric iron does not form complex ions with ammonium ions but nickel can form nickel ammonia complex ions with ammonium ions; and removing impurities from the nickel ammonia solution to prepare a nickel sulfate product. The invention has the advantages of short whole process flow, simple and convenient operation, low cost and high product value.
In particular, the present invention provides a method for preparing iron phosphate and nickel sulfate, the method comprising the steps of:
(1) Corroding and dissolving the alloy containing nickel and iron in electrolyte containing ammonium sulfate by adopting an electric auxiliary corrosion mode;
(2) After the electric auxiliary corrosion is completed, filtering the electrolyte to obtain filtrate;
(3) Adjusting the pH value of the filtrate obtained in the step (2), aerating, adding ammonium phosphate salt to generate ferric phosphate dihydrate precipitate, and filtering to obtain filtrate and ferric phosphate dihydrate;
(4) Adjusting the pH value of the filtrate obtained in the step (3), and filtering to remove impurity precipitate to obtain filtrate;
(5) Regulating the pH value of the filtrate obtained in the step (4), and evaporating to dryness to obtain residues;
(6) Acidolysis of the residue obtained in step (5) to obtain a solution;
(7) And (3) evaporating and crystallizing the solution obtained in the step (6) to obtain nickel sulfate.
In one or more embodiments, in step (1), the anode employed for the electro-assisted corrosion is a titanium coated lead dioxide basket anode.
In one or more embodiments, in step (1), the interpolar voltage of the electro-assisted corrosion is from 1 to 4V.
In one or more embodiments, in step (1), the electrically assisted corrosion is stopped when the concentration of ferrous ions in the electrolyte is greater than or equal to 50 g/L.
In one or more embodiments, in step (1), the pH of the electrolyte is controlled to 2 or less throughout the electro-assisted etching process.
In one or more embodiments, in step (1), the electrolyte further comprises sulfuric acid.
In one or more embodiments, in step (1), the electrolyte has a pH of from 0.5 to 1 at the beginning of the electro-assisted corrosion.
In one or more embodiments, in step (1), the nickel and iron containing alloy is nickel iron or water quenched nickel.
In one or more embodiments, in step (1), the alloy comprising nickel and iron is nickel iron; preferably, the ferronickel is bread iron; preferably, the nickel-iron or bread-iron is cut and then subjected to electrically assisted etching.
In one or more embodiments, in the step (3), the pH of the filtrate obtained in the step (2) is adjusted to 4.5 to 5.5.
In one or more embodiments, in step (3), the pH of the filtrate obtained in step (2) is adjusted to 4.5 to 5.5 by adding ammonium bicarbonate.
In one or more embodiments, in step (3), the ammonium phosphate salt is monoammonium phosphate.
In one or more embodiments, in the step (4), the pH of the filtrate obtained in the step (3) is adjusted to 6.5 to 7.5.
In one or more embodiments, in step (4), sodium hydroxide is added to the filtrate obtained in step (3) to adjust the pH of the solution to 6.5 to 7.5.
In one or more embodiments, in the step (5), the pH of the filtrate obtained in the step (4) is adjusted to 9 to 11.
In one or more embodiments, in step (5), sodium hydroxide is added to the filtrate obtained in step (4) to adjust the pH of the solution to 9 to 11.
In one or more embodiments, in step (6), acidolysis is performed using dilute sulfuric acid having a concentration of 30wt% to 70 wt%.
In one or more embodiments, the method further comprises: and (3) drying the ferric phosphate dihydrate obtained in the step (3) to obtain the ferric phosphate.
Drawings
FIG. 1 is a process flow diagram for preparing iron phosphate and nickel sulfate in some embodiments of the invention.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, "comprising," "including," "containing," and similar terms are intended to cover the meaning of "consisting essentially of … …" and "consisting of … …," e.g., "a consisting essentially of B and C" and "a consisting of B and C" should be considered to have been disclosed herein when "a comprises B and C" is disclosed herein.
In this document, all features such as values, amounts, and concentrations that are defined as ranges of values or percentages are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages, and proportions refer to mass ratios.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The method for preparing the ferric phosphate and the nickel sulfate comprises the following steps:
(1) Corroding and dissolving the alloy containing nickel and iron in electrolyte containing ammonium sulfate by adopting an electric auxiliary corrosion mode;
(2) After the electric auxiliary corrosion is completed, filtering the electrolyte to obtain filtrate;
(3) Adjusting the pH value of the filtrate obtained in the step (2), aerating, adding ammonium phosphate salt to generate ferric phosphate dihydrate precipitate, and filtering to obtain filtrate and ferric phosphate dihydrate;
(4) Adjusting the pH value of the filtrate obtained in the step (3), and filtering to remove impurity precipitate to obtain filtrate;
(5) Regulating the pH value of the filtrate obtained in the step (4), and evaporating to dryness to obtain residues;
(6) Acidolysis of the residue obtained in step (5) to obtain a solution;
(7) And (3) evaporating and crystallizing the solution obtained in the step (6) to obtain nickel sulfate.
In the present invention, an alloy containing nickel and iron is used as an iron source of iron phosphate and a nickel source of nickel sulfate. Useful nickel and iron containing alloys include nickel iron and water quenched nickel. In the invention, the ferronickel is a large steamed bread-shaped alloy containing nickel and iron, and the diameter of the ferronickel is generally more than 1cm. In the invention, the water-quenched nickel is small-particle irregular-pellet-shaped alloy containing nickel and iron, and the diameter of the water-quenched nickel is generally less than or equal to 1cm. In some embodiments, the nickel and iron-containing alloy used in the present invention is nickel iron. The use of ferronickel as a raw material has a cost advantage over water quenched nickel. In some embodiments, the present invention uses bread-like nickel iron (also known as bread iron). The nickel and iron-containing alloy used in the present invention has nickel and iron as main components, and the nickel content is usually not more than 15wt%. In some embodiments, the nickel content of the nickel and iron containing alloys used in the present invention is 5wt% to 15wt%, such as 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 12.5wt%, 13wt%, 14wt%. In some embodiments, the total content of nickel and iron in the nickel-and iron-containing alloy used in the present invention is ≡90wt%, for example ≡91wt%, ≡92wt%, ≡93wt%, ≡94wt%, ≡95wt%, ≡96wt%, and ≡97wt%. In addition to nickel and iron, the alloy containing nickel and iron may contain an impurity element, which may be one or more selected from Co, cr, si, al, ca, mg, mn and S, and the impurity element content is usually 5wt% or less, preferably 3wt% or less.
In the present invention, the electro-assisted corrosion (i.e., electrochemical corrosion) refers to dissolution of metal by means of an electric current in an electrolytic solution. In the present invention, the anode used for the electrically assisted corrosion is preferably a titanium-coated lead dioxide basket anode. The material of the cathode used for the electrically assisted etching is not particularly limited, and a general-purpose metal cathode may be used. The voltage between the electrochemical corrosion electrodes is between 1 and 4V, such as 2V and 3V. In the invention, the electrolyte used for electric auxiliary corrosion is an ammonium sulfate solution added with sulfuric acid, namely, the solute is an aqueous solution of sulfuric acid and ammonium sulfate. In step (1), the electrochemical corrosion actually occurs as follows:
anode reaction: fe/Ni-2e → Fe 2+ /Ni 2+
Cathode reaction: 2H (H) + +2e→H 2 ↑
In the state of normal-temperature acidic aqueous solution, the activities of iron and nickel are both greater than those of hydrogen, so that even if no voltage is applied, nickel and iron can spontaneously corrode in acidic ammonium sulfate solution. The invention adopts electric auxiliary corrosion and applies voltage for the following purposes: firstly, strengthening electrochemical corrosion and improving dissolution corrosion rate; second, under anodic strong oxidation conditions, elemental sulfur in an alloy containing nickel and iron (e.g., ferronickel) can be converted to sulfate that is present in solution without spilling out.
The electrolyte used in the invention contains ammonium sulfate and Fe which enters the solution 2+ And Ni 2+ Can be quickly complexed with ammonium to form ferrous ammino ion (Fe (NH) 3 ) 4 ] 2+ And nickel ammine ion [ Ni (NH) 3 ) 4 ] 2+ So that under the condition that ammonium ions are fully present, even if the chemical corrosion of nickel and iron consumes a large amount of H + The solution pH fluctuation is larger, the condition that Fe is deposited and attached on the surface of the anode due to the change of the solution pH is avoided, the corrosion of nickel and iron is more facilitated to be naturally carried out, and the power consumption is reduced. As electrochemical corrosion continues, the concentration of Fe and Ni in the electrolyte may continue to rise.
In the invention, the concentration of ammonium sulfate in the electrolyte at the beginning of the electric auxiliary corrosion is preferably 10-15 wt%, such as 11wt%, 12wt%, 13wt% and 14wt%, which is beneficial to avoiding the condition that Fe is deposited and attached on the surface of the anode due to the pH change of the solution, is beneficial to naturally carrying out the corrosion of nickel and iron, and reduces the power consumption. The pH of the electrolyte at the beginning of the electrically assisted corrosion is preferably 0.5 to 1, for example 0.6, 0.7, 0.8, 0.9, which is advantageous for the electrically assisted corrosion. The pH can be controlled by controlling the amount of sulfuric acid in the electrolyte.
In the whole electric auxiliary corrosion process, the pH value of the electrolyte is preferably controlled to be less than or equal to 2, which is beneficial to enhancing the conductivity and the iron-nickel solubility of the electrolyte and preventing the anodic polarization phenomenon in the electrochemical corrosion process. The pH may be controlled during the electro-assisted corrosion by adding sulfuric acid, e.g. dilute sulfuric acid, to the electrolyte. The addition of dilute sulfuric acid can enhance the conductivity and the iron-nickel solubility of the electrolyte and prevent the anodic polarization phenomenon in the electrochemical corrosion process. In the present invention, it is preferable to stop the electrically assisted corrosion when the concentration of the ferrous ions in the electrolyte is not less than 50 g/L.
In the step (2), the electrolyte obtained in the step (1) and dissolved with nickel and iron is filtered to remove suspended matters, and filtrate is obtained.
In the step (3), the filtrate obtained in the step (2) is aerated (air or oxygen is introduced for reaction) so that ferrous iron in the filtrate is converted into ferric iron. The pH during aeration can influence the reaction rate, the ferrous iron is not easy to combine with oxygen in the air to be converted into trivalent when the pH is less than 4.5, the formation of ferric iron can be accelerated when the pH is more than 5.5, the adsorption entrainment capacity is strong, the ferric phosphate sediment contains nickel adsorption impurities, and the purity of ferric phosphate dihydrate is influenced, so the pH of the filtrate obtained in the step (2) is adjusted to 4.5-5.5 (for example, 4.8, 5 and 5.2) and then aeration is carried out. In the step (3), the pH value of the electrolyte is regulated to 4.5-5.5, and ammonium phosphate salt is added, and Fe is utilized 3+ Characteristic of being unable to form complex ions with ammonium radical, fe 3+ In turn, the iron phosphate dihydrate is combined with phosphate to form ferric phosphate dihydrate sediment, and the reaction process is as follows:
4[Fe(NH 3 ) 4 ] 2+ +O 2 +4H + +2H 2 O→4Fe 3+ +4NH 3 ·H 2 O
2H 2 O+Fe 3+ +PO 4 3- →2H 2 O·FePO 4 ↓
in step (3), in order to avoid formation of ferric hydroxide precipitate, the pH of the filtrate obtained in step (2) is preferably adjusted to 4.5 to 5.5 by adding ammonium bicarbonate.
In step (3), the ratio of the amount of phosphate in the ammonium phosphate salt added to the amount of iron in the solution may be (0.9 to 1.1): 1, for example 0.95:1, 0.98:1, 1:1, 1.02:1, 1.05:1. The ammonium phosphate salt added in step (3) is preferably ammonium dihydrogen phosphate, since ammonium dihydrogen phosphate is relatively inexpensive and less ammonium is introduced than other phosphates, and the subsequent ammonia distillation is low in cost. In the step (3), ammonium phosphate salt is added to convert iron ions into ferric phosphate dihydrate for precipitation, and then the ferric phosphate dihydrate and filtrate are obtained through filtration.
In the step (4), the pH of the filtrate obtained in the step (3) is adjusted to 6.5-7.5, for example, 6.8, 7 and 7.2, so that impurities such as iron are converted into precipitate, and the precipitate is filtered to remove iron deeply, thereby obtaining filtrate. Since iron cannot be effectively precipitated at a pH < 6.5, a pH > 7.5 will result in precipitation of nickel, and the pH of the filtrate is adjusted to 6.5-7.5 in step (4). Sodium hydroxide may be used to adjust the pH of the filtrate to 6.5 to 7.5, preferably sodium hydroxide in the form of liquid alkali. The impurity removal in the step (4) can effectively improve the purity of the nickel sulfate product, reduce the impurity content of the nickel sulfate product and enable the nickel sulfate product to meet the requirements of battery grade nickel sulfate.
In the step (5), the pH of the filtrate obtained in the step (4) is adjusted to 9 to 11, for example, 9.5, 10, 10.5. In the step (5), the pH is adjusted to 9-11 because ammonium ions in the solution cannot exist stably under alkaline conditions, nickel can be left by ammonia distillation, and too high pH can increase the dosage of a pH regulator (such as sodium hydroxide) and dilute sulfuric acid in the subsequent dissolution of nickel slag, thereby causing cost increase. Sodium hydroxide may be used to adjust the pH of the filtrate to 9 to 11, preferably sodium hydroxide in the form of liquid alkali. After adjusting the pH, the solution may be placed in a negative pressure evaporator (e.g., a rotary evaporator) to heat and evaporate the ammonia. The overflow ammonia gas may be absorbed with dilute sulfuric acid or an acidic ammonium sulfate solution (e.g., an ammonium sulfate solution containing sulfuric acid). In some embodiments, the negative pressure evaporator maintains absolute pressure less than or equal to 1500Pa until the temperature in the negative pressure evaporator rises to 80-100 ℃ and no volatiles are off.
In the step (6), the ammonia distillation residue obtained in the step (5) is acidolyzed by dilute sulfuric acid to obtain a nickel sulfate solution. Preferably, the acidolysis is carried out using dilute sulfuric acid having a concentration of 30wt% to 70wt%, for example 40wt%, 50wt%, 60 wt%.
In the step (7), the nickel sulfate solution obtained by acidolysis is evaporated and crystallized to obtain the nickel sulfate. The nickel sulfate prepared by the method is battery grade nickel sulfate. Herein, battery grade nickel sulfate refers to nickel sulfate that meets the HG/T5919-2021 standard.
The invention may further comprise step (8): and (3) drying the ferric phosphate dihydrate obtained in the step (3), and then finely grinding to obtain the ferric phosphate. The ferric phosphate prepared by the method is battery grade ferric phosphate. Herein, battery grade iron phosphate refers to iron phosphate meeting HG/T4701-2021 standard.
The method solves the problem of preparing two battery materials, namely ferric phosphate and nickel sulfate by taking the alloy containing nickel and iron as raw materials, and particularly ensures that the bread iron can also be used as the raw materials and is compatible with water quenching nickel raw materials. In the invention, due to the action of electrochemical corrosion, a small amount of sulfur in the alloy containing nickel and iron (such as ferronickel) can not form hydrogen sulfide overflow when dissolved by the action of acid, and the operation is environment-friendly. Compared with the existing process for preparing ferric phosphate and nickel sulfate, the invention introduces the coordination complex of ammonium sulfate and the selective precipitation characteristic of ammonium phosphate, avoids the problem that impurity metal ions cannot be separated in the ferrous sulfate and ammonium hydrogen phosphate method, only 3-valent iron ions and phosphate form ferric phosphate dihydrate precipitation, and directly realizes the aim of preparing the high-quality ferric phosphate product by using iron existing in the alloy containing nickel and iron (such as ferronickel). The invention adopts ammonia distillation and sulfuric acid or acidic ammonium sulfate solution to absorb volatile ammonia gas, thus realizing the large circulation of ammonia in the whole comprehensive utilization process of nickel-iron-containing alloy (such as ferronickel), and no pollution wastewater is discharged.
The invention will be illustrated by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods, reagents and materials used in the examples are those conventional in the art unless otherwise indicated. The starting compounds in the examples are all commercially available.
Example 1
This example uses the battery grade iron phosphate and nickel sulfate preparation method shown in fig. 1 to prepare battery grade iron phosphate and nickel sulfate.
This example uses bread-iron-like ferronickel having a nickel content of 12wt% as a raw material, and its elemental composition is shown in table 1.
Table 1: elemental composition of Nickel-iron used in example 1
The preparation process of example 1 comprises the following steps:
step 1: sulfuric acid and ammonium sulfate were dissolved in water to prepare 5L of an ammonium sulfate solution (ammonium sulfate mass concentration: 13 wt%) having a pH of 0.8; cutting ferronickel into square strips with the width of 1cm, and placing the square strips in an anode frame, wherein the anode frame is a lead dioxide basket type anode coated with titanium; placing a cathode plate and an anode frame in an ammonium sulfate solution serving as electrolyte; direct current is conducted between the cathode and the anode, the voltage between the electrochemical corrosion electrodes is controlled to be 2V, and the electrochemical corrosion is continued; in the electrochemical corrosion process, continuously circulating electrolyte by a pump, and adding sulfuric acid to control the pH of the electrolyte to be less than 2;
step 2: when the concentration of ferrous ions in the electrolyte reaches 50g/L, taking out the anode frame and the cathode, and carrying out suction filtration on the electrolyte to obtain a clear solution;
step 3: regulating the pH value of the clarified solution obtained in the step 2 to 4.5 by using ammonium bicarbonate, aerating, gradually adding ammonium dihydrogen phosphate saturated solution, wherein the mass of ammonium dihydrogen phosphate in the solution is 520g, generating ferric phosphate dihydrate precipitate, and filtering and separating ferric phosphate dihydrate from the solution to obtain filtrate;
step 4: regulating the pH value of the filtrate produced in the step 3 to 7 by liquid alkali, and filtering to remove impurities to obtain filtrate;
step 5: regulating the pH value of the filtrate obtained in the step 4 to 10 by liquid alkali, and evaporating in a rotary evaporator until the temperature in the rotary evaporator rises to 100 ℃ and no volatile matters are cut off, wherein the absolute pressure of the rotary evaporator is maintained to be less than or equal to 1500Pa, and absorbing volatile matters (ammonia gas) by dilute sulfuric acid;
step 6: dissolving the dried nickel mud in the rotary evaporator by dilute sulfuric acid with the concentration of 30wt%, and acidolysis until the nickel mud is clear and transparent;
step 7: evaporating, concentrating and crystallizing the solution obtained by acidolysis in the step 6, and filtering to obtain a battery-grade nickel sulfate product; the detected nickel sulfate product composition is shown in table 2 ("ND" indicating not detected);
table 2: EXAMPLE 1 Nickel sulfate product composition test results
Step 8: placing the ferric phosphate dihydrate obtained in the step 3 into an oven, adjusting the drying temperature to 240 ℃ and drying for 12 hours at constant temperature, and grinding to obtain a battery grade ferric phosphate product; the iron phosphate product ingredients tested are shown in table 3 ("ND" indicating not tested);
table 3: EXAMPLE 1 iron phosphate product ingredient test results
Example 2
Example 2 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron starting material and preparation method used in example 1, except that the pH of the solution was adjusted to 5.5 with ammonium bicarbonate in step 3.
Example 3
Example 3 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron starting material and preparation method used in example 1, except that the pH of the solution was adjusted to 6.5 with ammonium bicarbonate in step 4.
Example 4
Example 4 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron starting material and preparation method used in example 1, except that the pH of the solution was adjusted to 7.5 with ammonium bicarbonate in step 4.
Example 5
Example 5 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron starting material and preparation method used in example 1, except that the pH of the solution was adjusted to 9 with ammonium bicarbonate in step 5.
Example 6
Example 6 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron starting material and preparation method used in example 1, except that the pH of the solution was adjusted to 11 with ammonium bicarbonate in step 5.
Various indexes of the nickel sulfate products obtained in the examples 2-6 still accord with the solid type II standard of the battery grade nickel sulfate product, and the purity of the iron phosphate products obtained in the examples 2-6 is the type II standard of the battery grade ferric phosphate dihydrate product.
Comparative example 1
Comparative example 1 battery grade iron phosphate and nickel sulfate were prepared using the nickel iron raw material and the preparation method used in example 1, except that step 4 in example 1 was omitted.
The preparation process of comparative example 1 comprises the following steps:
step 1: sulfuric acid and ammonium sulfate were dissolved in water to prepare 5L of an ammonium sulfate solution (ammonium sulfate mass concentration: 13 wt%) having a pH of 0.8; cutting ferronickel into square strips with the width of 1cm, and placing the square strips in an anode frame, wherein the anode frame is a lead dioxide basket type anode coated with titanium; placing a cathode plate and an anode frame in an ammonium sulfate solution serving as electrolyte; direct current is conducted between the cathode and the anode, the voltage between the electrochemical corrosion electrodes is controlled to be 2V, and the electrochemical corrosion is continued; in the electrochemical corrosion process, continuously circulating electrolyte by a pump, and adding sulfuric acid to control the pH of the electrolyte to be less than 2;
step 2: when the concentration of ferrous ions in the electrolyte reaches 50g/L, taking out the anode frame and the cathode, and carrying out suction filtration on the electrolyte to obtain a clear solution;
step 3: regulating the pH value of the clarified solution obtained in the step 2 to 4.5 by using ammonium bicarbonate, aerating, gradually adding ammonium dihydrogen phosphate saturated solution, wherein the mass of ammonium dihydrogen phosphate in the solution is 520g, generating ferric phosphate dihydrate precipitate, and filtering and separating ferric phosphate dihydrate from the solution to obtain filtrate;
step 4: regulating the pH of the filtrate obtained in the step 3 to 10 by liquid alkali, and evaporating in a rotary evaporator until the temperature in the rotary evaporator rises to 100 ℃ and no volatile matter is cut off, wherein the absolute pressure of the rotary evaporator is maintained to be less than or equal to 1500Pa, and absorbing volatile matter (ammonia gas) by dilute sulfuric acid;
step 5: dissolving the dried nickel mud in the rotary evaporator by dilute sulfuric acid with the concentration of 30wt%, and acidolysis until the nickel mud is clear and transparent;
step 6: evaporating, concentrating and crystallizing the solution obtained by acidolysis in the step 5, and filtering to obtain a nickel sulfate product; the detected nickel sulfate product composition is shown in table 4 ("ND" indicating not detected);
table 4: comparative example 1 Nickel sulfate product composition test results
Step 7: and (3) placing the ferric phosphate dihydrate obtained in the step (3) into an oven, adjusting the drying temperature to 240 ℃ and drying for 12 hours at constant temperature, and grinding to obtain a battery grade ferric phosphate product.
It should be noted that the embodiment provided in the present invention is only one way of optimizing the effect, and does not limit the present invention itself.
The foregoing has outlined and described the technical objects, basic principles, main features and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing description merely illustrates the principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (11)
1. A method of preparing iron phosphate and nickel sulfate, the method comprising the steps of:
(1) Corroding and dissolving the alloy containing nickel and iron in electrolyte containing ammonium sulfate and sulfuric acid by adopting an electric auxiliary corrosion mode;
(2) After the electric auxiliary corrosion is completed, filtering the electrolyte to obtain filtrate;
(3) Adjusting the pH value of the filtrate obtained in the step (2) to 4.5-5.5, aerating, adding ammonium phosphate salt to generate ferric phosphate dihydrate precipitate, and filtering to obtain filtrate and ferric phosphate dihydrate;
(4) Regulating the pH value of the filtrate obtained in the step (3) to 6.5-7.5, and filtering to remove impurity precipitate to obtain filtrate;
(5) Regulating the pH value of the filtrate obtained in the step (4) to 9-11, and evaporating to dryness to obtain residues;
(6) Acidolysis of the residue obtained in step (5) to obtain a solution;
(7) And (3) evaporating and crystallizing the solution obtained in the step (6) to obtain nickel sulfate.
2. The method according to claim 1, wherein in the step (1), the anode used for the electro-assisted corrosion is a lead dioxide basket anode coated with titanium, the inter-electrode voltage of the electro-assisted corrosion is 1-4V, the electro-assisted corrosion is stopped when the concentration of ferrous ions in the electrolyte is more than or equal to 50g/L, and the pH of the electrolyte is controlled to be less than or equal to 2 in the whole electro-assisted corrosion process.
3. The method according to claim 1, wherein in the step (1), the pH of the electrolyte at the start of the electrically assisted corrosion is 0.5 to 1.
4. The method of claim 1, wherein in step (1), the nickel-and iron-containing alloy is nickel-iron or water quenched nickel.
5. The method of claim 1, wherein in step (1), the alloy comprising nickel and iron is nickel iron.
6. The method according to claim 1, wherein in the step (3), the pH of the filtrate obtained in the step (2) is adjusted to 4.5 to 5.5 by adding ammonium bicarbonate.
7. The method of claim 1, wherein in step (3), the ammonium phosphate salt is monoammonium phosphate.
8. The method according to claim 1, wherein in the step (4), sodium hydroxide is added to the filtrate obtained in the step (3) to adjust the pH of the solution to 6.5 to 7.5.
9. The method according to claim 1, wherein in the step (5), sodium hydroxide is added to the filtrate obtained in the step (4) to adjust the pH of the solution to 9 to 11.
10. The method according to claim 1, wherein in the step (6), the acidolysis is performed using dilute sulfuric acid having a concentration of 30 to 70 wt%.
11. The method according to claim 1, wherein the method further comprises: and (3) drying the ferric phosphate dihydrate obtained in the step (3) to obtain the ferric phosphate.
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